EP0578983A1 - Procédé de préparation d'hydrides d'étain trialkylique - Google Patents

Procédé de préparation d'hydrides d'étain trialkylique Download PDF

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Publication number
EP0578983A1
EP0578983A1 EP93109590A EP93109590A EP0578983A1 EP 0578983 A1 EP0578983 A1 EP 0578983A1 EP 93109590 A EP93109590 A EP 93109590A EP 93109590 A EP93109590 A EP 93109590A EP 0578983 A1 EP0578983 A1 EP 0578983A1
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EP
European Patent Office
Prior art keywords
nabh4
trialkyltin
process according
bis
hydrides
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP93109590A
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German (de)
English (en)
Other versions
EP0578983B1 (fr
Inventor
Ralf-Jürgen Dr. Dipl.-Ing. Becker
Ulrich Dr. Dipl.-Chem. Stewen
Udo Chem. Weinberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemtura Organometallics GmbH
Original Assignee
Witco GmbH
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Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen

Definitions

  • the present invention relates to an improved process for the preparation of trialkyltin hydrides of the general formula R1R2R3SnH, which, due to the process control, have excellent storage stability.
  • Organotin hydrides are valuable and extremely versatile reagents for organic synthesis. This is demonstrated by a large number of publications. Detailed information can be found in some reviews, e.g. B. W. P. Neumann, Synthesis 1987, 665; B. Giese, Radicals in Organic Synthesis: Formation of Carbon Bonds, Pergamon Press, Oxford 1986; M. Pereyre, J.P. Quintard and A. Rahm: Tin in Organic Synthesis, Butterworth, London 1987; D.P. Curran, Synthesis 1988, 417, 489; I. Omar, Organotin Chemistry, Elsevier, Amsterdam 1989; P.G. Harrison, Chemistry on Tin, Blackie, Glasgow and London 1989.
  • the instability is caused in particular by traces of impurities which remain in the product as a result of the production and act directly as decomposition catalysts. So cause traces of Lewis acids, such as. B. aluminum halides, boron halides, organoaluminium and organotin halides, the immediate decomposition.
  • US-A-4 282 166 describes a process for the preparation of trialkyltin hydrides from trialkyltin chloride and sodium bis (2-alkoxyethoxy) aluminum dihydride.
  • CA 90: 204.205 p describes the reduction of trialkyltin chloride with NaBH4 in ether-water mixtures with yields of 65 - 80%.
  • alkyltin oxides and chlorides can be converted to tin hydrides (K. Hayashi et al, J. Organomet. Chem., 10 (1), 81-94; JP 43.010.134 (CA 69: 106.880 b); JP 43.010.133 (CA 69: 106.879 h); JP 43.012.132 (CA 70: 37 922 y); DE 3 119 643).
  • LiAIH4 provides trialkyltin hydrides in yields between 66 - a maximum of 89% (HJ Albert, TN Mitchell, WP Neumann, Methodicum Chimicum, H. Zimmer, Ed., Vol. 7, Part A, Academic Press, New York, 1977, 361-2).
  • Trialkyltin chlorides can be reacted in good yields with NaBH,, the reaction and the workup are complex and cumbersome (J. Organomet. Chem., 9 (2), 379-82 (1967).
  • Patent HU-A-41.412 describes a process for the preparation of tri-n-butyltin hydride from bis- [tri-n-butyltin] oxide, which is characterized in that bis- [tri-n-butyltin] oxide in an aliphatic alcohol dissolves and can react at a temperature of 10 - 30 ° C with an alcoholic and / or aqueous NaBH4 solution for 10 - 60 min. After complex cleaning steps, tri-n-butyltin hydride is isolated in yields between 64-84%.
  • the process according to the invention allows, starting from inexpensive, readily available starting compounds, the production of high-purity qrganotin hydrides in quantitative yield, which, apparently due to the extraction and neutralization effect, are free of decomposition initiators or catalysts.
  • an inert solvent is advantageously chosen which does not react either with organotin hydrides or with NaBH4.
  • Suitable solvents are diethyl ether, dioxane, acetonitrile, hydrocarbons, preferably tetrahydrofuran.
  • the starting compounds are preferably used in a stoichiometric or approximately stoichiometric ratio in the range from 0.5 to 1.5 mol NaBH4 to 1 mol bis- [trialkyltin] oxide.
  • a stabilized aqueous NaBH4 solution is advantageously used for safe handling, for which bases such as sodium hydroxide are particularly suitable.
  • hydrogen-acidic compounds such as thiosalicylic acid, lactic acid, lauryl mercaptan, preferably thioglycolic acid, are preferably added.
  • antioxidants are also advantageous.
  • Typical radical scavengers can be used for this, such as. B. BHT (2,6-di-tert-butyl-4-methylphenol), 3-tert-butyl-4-hydroxyanisole, pyrogallol and / or typical metal ion deactivators, such as. B. triphenylphosphine, 4,4-thiobis (2-tert-butyl-5-methylphenol), ethylenediamine-N, N, N ', N'-tetra-2-propanol, N', N'-diphenyl-1,4-phenylenediamine.
  • reaction of bis- [trialkyltin] oxides with an aqueous, stabilized NaBH4 solution can be easily controlled by controlled metering in of the reducing agent.
  • the reverse reaction, i.e. Presentation of the NaBH4 solution is possible without loss of yield.
  • the reaction can be carried out either continuously or batchwise.
  • the upper organic phase contains the trialkyltin hydride and, if the metering has not ended, the unreacted bis- [trialkyltin] oxide.
  • the lower aqueous phase contains the reducing agent NaBH4 and its oxidation products.
  • the lower aqueous phase is separated and can, for. B. be used again after enrichment with NaBH4.
  • the solvent is distilled off from the upper organic phase, which contains the organotin hydride. There is no additional cleaning of the product.
  • trialkyltin hydrides can be prepared in highly pure form and in almost quantitative yield by the extraction and neutralization effect of the basic aqueous phase.
  • the trialkyltin hydrides are free of decomposition initiators or catalysts without additional purification and therefore have excellent storage stability.
  • Tributyltin hydride is isolated in approximately quantitative yield from the reaction analogous to Example 1, but with the additional use of 3% BHT.
  • reaction conditions are chosen analogously to Example 5. Lactic acid is used as an accelerator instead of thiosalicylic acid.
  • reaction conditions are chosen analogously to Example 5. Instead of thiosalicylic acid, lauryl mercaptan is used as an accelerator.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Steroid Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP93109590A 1992-07-17 1993-06-16 Procédé de préparation d'hydrides d'étain trialkylique Expired - Lifetime EP0578983B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4223615A DE4223615A1 (de) 1992-07-17 1992-07-17 Verfahren zur Herstellung von Trialkylzinnhydriden
DE4223615 1992-07-17

Publications (2)

Publication Number Publication Date
EP0578983A1 true EP0578983A1 (fr) 1994-01-19
EP0578983B1 EP0578983B1 (fr) 1998-02-18

Family

ID=6463494

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93109590A Expired - Lifetime EP0578983B1 (fr) 1992-07-17 1993-06-16 Procédé de préparation d'hydrides d'étain trialkylique

Country Status (10)

Country Link
US (1) US5288886A (fr)
EP (1) EP0578983B1 (fr)
JP (1) JP3338130B2 (fr)
AT (1) ATE163292T1 (fr)
AU (1) AU659005B2 (fr)
CA (1) CA2098213C (fr)
DE (2) DE4223615A1 (fr)
DK (1) DK0578983T3 (fr)
ES (1) ES2114970T3 (fr)
MX (1) MX9304278A (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5877336A (en) * 1996-12-31 1999-03-02 Bridgestone Corporation Synthesis of tributyltin lithium
JP2009525939A (ja) * 2006-02-08 2009-07-16 ロス アラモス ナショナル セキュリティ，リミテッド ライアビリテイ カンパニー ボラン類のエネルギー効率の良い合成

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1381395A (fr) * 1962-10-19 1964-12-14 Studiengesellschaft Kohle Mbh Procédé pour la stabilisation d'hydrures organo-stanniques

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1468709A1 (de) * 1960-11-08 1969-05-08 Studiengesellschaft Kohle Mbh Verfahren zur Stabilisierung von Organozinnhydriden
DE1167345B (de) * 1960-11-08 1964-04-09 Studiengesellschaft Kohle Mbh Verfahren zur Stabilisierung von Organozinnhydriden
US3401183A (en) * 1965-12-23 1968-09-10 Gen Electric Method for preparing organo germanium, tin and silicon hydrides
US3439008A (en) * 1966-03-31 1969-04-15 Gen Electric Method for making organometallic hydrides
US4282166A (en) * 1980-04-11 1981-08-04 Argus Chemical Corporation Preparation of lower trialkyltin hydride from trialkyltin chloride
DE3119643A1 (de) * 1981-05-16 1982-12-02 Paul Rauschert Gmbh & Co Kg, 8644 Pressig Zinnorganische verbindungen, verfahren zu deren herstellung und deren verwendung

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1381395A (fr) * 1962-10-19 1964-12-14 Studiengesellschaft Kohle Mbh Procédé pour la stabilisation d'hydrures organo-stanniques

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMISTRY & INDUSTRY Bd. 23, 1988, Seite 764 J. SZAMMER ET AL *
DATABASE WPIL Week 8721, Derwent Publications Ltd., London, GB; AN 87-145433 *
SYNTHESIS Bd. 9, 1983, Seite 722 A.B. CHOPA ET AL *

Also Published As

Publication number Publication date
JPH06179687A (ja) 1994-06-28
CA2098213C (fr) 1997-12-16
JP3338130B2 (ja) 2002-10-28
ES2114970T3 (es) 1998-06-16
DE4223615A1 (de) 1994-01-20
AU3981893A (en) 1994-01-20
AU659005B2 (en) 1995-05-04
DK0578983T3 (da) 1998-09-28
US5288886A (en) 1994-02-22
CA2098213A1 (fr) 1994-01-18
EP0578983B1 (fr) 1998-02-18
MX9304278A (es) 1994-08-31
DE59308155D1 (de) 1998-03-26
ATE163292T1 (de) 1998-03-15

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